Insecticidal composition



Patented Dec. 1, 1942 UNITED STATES PATENT' OFFICE INSECTICIDAL COMPOSITION Gerald E. Coleman and Fred w Fletcher- Midland, Mich., assignors to The Dow Chemical Company, Midland, Mlcln, a corporation of Michigan No Drawing. Application January 15, 1941, Serial No. 374,556

9 Claims.

ployed as constituents of dusting mixtures, petroleum distillate sprays, or in aqueous dispersion. Pyrethrin-containing compositions have a quick paralyzing action on flies and other insects but give a relatively low kill as compared to the per cent knockdown. With rotenone a high moribund kill is generally obtained, although a considerable period of time is required to destroy insect pests. The plant extracts are generally unstable to heat and light and 'lose their efiectiveness to a considerable degree upon storage.

We have discovered that mixtures of one or more of these plant extract toxicants with certain ether compounds have a greatly increased effectiveness against insect pests. The group of phenolic ethers employed in such toxicant mixtures according to the present invention are those having the following formula R OCnH2n-X wherein It represents an aromatic radical, X is chlorine or bromine, and n is an integer greater than 1. A preferred group of compounds falling within the scope of the foregoing formula are those in which n is an integer from 2 to 4, inclusive.

Dust and spray compositions comprising as an effective toxicant such a mixture of pyrethrins and/r rotenone with one or more of the foregoing synthetic ether compounds are more stable toheat and light and have a greater paralyzing effect and a greater lethal efiect on insects than do compositions comprising an equivalent amount of the plant extract toxicants alone. By employing such combinations of parasiticidal materials, significant economies in the amounts of pyrethrin and/or rotenone required are efiected. In such compositions the synthetic ether comwith the particular materials concerned, the type of composition in which such toxicant mixture is to be employed, and the nature of the insect or mite pest to be controlled. Generally speaking, a concentration of'from about 0.5 to

5 grams of the ether compound per 100 grams of the finished insecticidal composition is sufilcient. The amounts of rotenone or pyrethrins employed may be those common to spraying and dusting practices, although appreciably smaller amounts are operable where a result comparable to that obtained with the plant extract toxicant alone is desired.

The aromaticoxy-alkyl halides with which the present invention is concerned are conveniently prepared by reacting phenols with dihalogensubstituted parafiin hydrocarbons in the presence of aqueous sodium hydroxide. In,carrying out such reaction, an excess of the dihalo-paraflin hydrocarbon is reacted with substantially equimolecular proportions of the caustic and phenol. The reactants are mixed together with heating and stirring to a reaction temperature generally between about 80 and 150 C., depending upon the reactivity of the dihalo paraflin hydrocarbon employed. When the reaction is complete, the

mixture is cooled, extracted with a suitable water-immiscible organic solvent, and the extract fractionally distilled, whereby the aromaticoxy-alkyl halide is obtained in good yield. Both the monoand di-substltuted derivatives of the dihalo paraffin hydrocarbon are generally produced in the reaction, the excess of the halogenated hydrocarbon favoring the formation of the obtained are low-melting solids or relatively high-boiling water-insoluble liquids, and are submono-substituted product. The compounds so and are not to be construed as limiting the inpounds and the rotenone or pyrethrin so supple- 'ment one another as to result in a greater than additive control of insect pests. That is to say, a synergistic efiect is obtained.

The exact amounts of pyrethrins and/or rotenone employed and the proportion of synvention:

EXAMPLE 1 A standard pyrethrin extract was dissolved in a petroleum distillate having a boiling range of 345-508 F. and a flash point of 137 F. in amount suflicient that each milliliters of .the ultimate solution contained 50 milligrams of pyrethrins.

thetic ether compound mixed therewith varies 5 solution. The several comp 50 Obtained were tested according to the Peet-Grady method (Soap 8, No. 4, 1932. pages 98-102 and 121) to asoaces phenoxy)-ethyi chloride, beta-(2.4-dichlorophenoxy)-ethyl chloride, beta-('-tertiarybutyldetermine their efficiency against three-day old phenoxy) -ethyl chloride, beta-(2.6-dichloro-4- houseflies. To provide basis for the comparison tertiarybutyl-phenoxy)-ethyl chloride, beta-(2- of the efilciency of such mixtures with the efli- 5 xenoxy) -ethyl chloride, beta-(4 1 ciencies of the several individual toxicants emnoxy) -ethyl I bromide, gamma-(2,4,6-tr1cb1g ployed therein, control determinations were made phenoxy) -propyl chloride, g amma-(-chlorowith the base solution alone and with solutions phenoxy) -isobutyi chloride, gamma-(i-bromoof the several aromaticoxy-alkyl halides at 2.5 phenoxy) -isobutyi chloride, gamma-(zt grams per 100 co. in the petroleum distillate. w phenoxy) -isobutyl chloride, gamma-(beta-naph- The following table sets forth the results obtained thoxy) -isobutyi chloride, beta-(4-xenoxy) -isowith representative mixtures: butyl chloride, delta-(2-cyclohexyl-phenoxy) -n- Table 2.5 grams of other 2 g g gg rugs. pyrcthrins compound plus 100 cm petroleum r 100 cc. tro- 50 mgs. pyrethrin distillate cum dist etc get 111 cc. pctro' Name oi compound um distillate Knock- Knock- Knock- Kill in Kill in Kill in down 10 down 10 d 10 minutes 48 hours minutes 48 hours ga 48 hours Beta-(abmmohenoxy)ethyl bromide (melting at 5556 28. 9 5.8 95 27 9, 3 L 7 Gemma-(4-bromo-phenoxy)-progyl bromide (melting at 4546 C 45.6 14. 5 96 27 97. 2 52. 3 Beta-(4-bromo-phenoxy)-cthyl c loride (melting at 5858.5 34. 0 8.0 95 27 98. 4 41. l Gamma-(4-bromo-phenoxy)-propyi chloride (melting at 44-45 65.4 8.0 95 27 98.4 40.0 Gamma-(2-cl1loro-4-cyclohexyl-phenoxy)-propyl chlorrde- (borlmg at 165 168 C. at 2 millimeters pressure and having a specific gravity of 1.168 at 20 4 0.) 45.6 5.1 as. c 35.9 99.1 58. 3 Beta-(2-chloro-4-tertiarybutyl-phenoxy)-ethyl chloride (boil ng at 150 7 151 C. at 6 millimeters pressure and having a specific gravity oi 1.150 at 20 4C 71.6 9.7 98.6 35.9 97.7 60.3 Beta-phenoXy-ethyl chloride (boiling at l05l07 C. at 10 millimeters pressure and having a specific gravity of 1.153 at i 40. 8 2.6 98. 6 35.9 100 44, 3 B t (2 4 6-trich1oro-phenoxy)-ethyl chloride (melting Bt 3 1 6 6-0 93- 6 35.9 99. 5 47-2 Gamme-(4-tertiarybutyl-phenoxy)-isobutyl chloride (boiling at 1l0l12 C.

at 2 millimeters pressure and having a specific gravity of 1.023 at 20l4 G.).. 61. 8 i0. 7 98. 0 35,9 99. 2 54. 0

In each of the determinations as set forth above, the pyrethrin solution alone was found to give a kill on flies much less than that required for a commercial insecticidal product. Also each of the aromaticoxy-alkyl halides alone was unsatisfactory. The compositions embodying the combination of toxicant materials, however, gave a control of flies falling within the range recommended for household insecticide materials, such degree of control being greater than additive with respect to the controls obtained with the individual components of the mixtures.

EXAMPLE H A dustcomposition comprising the new toxicant mixture and adapted to be employed for the control of such agricultural pests as pea aphis has the following composition:

- Parts by weight Gamma-K4-,tertiarybutyl-phenoxy) isobutyl chloride 1.5 Derris resins 0.5 Walnut shell flour 98.0

Among other compounds which may be compounded with pyrethrinand/or rotenone-containing plant extracts and employed in standard type insecticidal compositions are beta- (4-chloro- E8 butyl bromide, beta-( i-benzyl-phenoxy) -n-amyl chloride, omega-phenoxy-n-octyl chloride, etc. The new toxicant mixtures with which the present invention is concerned may be used also as toxicants in emulsions and in combination with soap or other wetting, emulsifying, or detergent agents. Various perfumes or coloring agents may be employed therewith if desired. Besides petroleum distillates; such organic solvents as benzene, ethylene chloride, hydrogenated naphthalene, butyl alcohol, ketones, etc. may be employed as carriers for the toxicant mixtures. The phrase non-corrosive organic solvent as employed in certain of the following claims refers to any organic solvent material unreactive with and capable of dissolving the toxicants described and non-injurious to the skin and general health of humans.

Common dust carriers which may be employed in combination with the toxicant mixtures are diatomaceous earth, volcanic ash, bentonite, redwood flour, kieselguhr, white talc, and the like.

We claim:

1. An insecticidal composition comprising as an active toxicant a mixture of a material of the class consisting of rotenoneand pyrethrin-containing plant extracts with a compound having the formula wherein R represents an aromatic radical, X represents a member of the group consisting of chlorine and bromine, and n is an integer from where R represents an aromatic radical, X represents a member of the group, consisting of chlorine and bromine, and n is an integer from 2 to 8, inclusive, and wherein the synthetic ether compound is present in the amount of at least 0.5 gram per 100 grams of composition.

3. An insecticidal composition comprising a mixture of pyrethrins and a compound having wherein R represents an aromatic radical of the benzene series, X -represents a member of the group'consisting of chlorine and bromine, and n is an integer from 2 to 4, inclusive.

5. An insecticidal composition comprising a mixture of a material of the class consisting of rotenoneand pyrethrin-containing plant extracts with a compound having the formula wherein R represents an aromatic radical of the benzene series, X represents a member of the group consisting of chlorine and bromine, and n is an integer from 2 to 4, inclusive, and wherein the synthetic ether compound is present in the amount or at least 0.5 gram per 100 grams of composition.

6. An insecticidal spray comprising a non-corroslve organic solvent and having dissolved therein a mixture of a pyrethrin-containingplant ,extract with a compound having the formula wherein R represents an aromatic radical, X represents a member of the group consisting of chlorine and bromine, and n lsan integer from 2 to 8, inclusive.

7. An insecticidal composition comprising as an active toxioant a mixture of a material of the class consisting of rotenoneand pyrethrin-containing plant extracts with a compound having the formula wherein R represents an aromatic radical, and n is an integer from 2 to 8, inclusive.

8. An insecticidal composition comprising as.

an active toxicant a mixture of a material of the class consisting of rotenoneand pyrethrimcontaining plant extracts with a compound having the formula wherein R. represents an aromatic radical, and 'n is an integer from 2 to 8, inclusive.

' 9. An insecticidal composition comprising as an active toxicant a mixture of a material of the class consisting of rotenoneand pyrethrin-containlng plant extracts with a compound having the formula 4 wherein R represents an aromatic radical of the benzene series, and X represents a member or the group consisting of chlorine and bromine.

GERALD H. COLEMAN. FRED W. FIETCEW... 

